DE2520526A1 - NEW CHROME COMPLEX DYES, THEIR PRODUCTION AND USE - Google Patents

Description

CLBA-GEIGY AG, CH -4002 Basel

CiBA-GElGY

Case 1-9402 / 1 + 2 Germany

Attorney file 25 905

DR. BERG D IPL.-ING. STAPF

DlPL.-1NG. SWATCH DB. DR. SANDMAIR

PATENTANWÄLTE 9 MÖNCHEN 60 ■ MAUEFWURCHERSTR ^

May 7th 1975

New chromium complex dyes, their production and use.

The present invention relates to 1: 2 chromium complex dyes the formula

(N

J = N-Ar-N = N-Ar ¹ )
N = N-Ar ")

(D

wherein

A is the residue of a diazo component of the benzene or naphthalene series, which the complex-forming group X in ο position to the azo group,

B the remainder of a coupling in the o-position to the oxy group Coupling component means

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D is the remainder of an amine of the benzene or naphthalene series, which is the complex-forming group in the o-position to the azo group wearing,

X is an oxygen atom or "a -CO-O- group, Ar is an aromatic carbocyclic radical, Ar ¹ and Ar" is an aromatic, carbo- or heterocyclic radical, q is an integer from 0 to 5, η is an integer from 1 to 3 , m is an integer from 0 to 2 and ρ is 0 or 1

mean, where n + m may be at most 3 and in which the benzene ring a can carry a further fused-on benzene ring or can be substituted by halogen, nitro, alkyl and alkoxy, in particular low molecular weight alkyl and alkoxy, and K is a cation.

The term "low molecular weight ¹¹ " refers to groups with 1 to 4 carbon atoms; the term "aryl" means in particular phenyl and phenyl substituted with halogen, nitro, low molecular weight alkyl or alkoxy, and "aralkyl" means primarily the benzy group .

The dyes of the formula (1) are obtained by adding a dye of the formula

A N = N B

XH OH ^ΚΔ '

(3)

where the symbols A, B, X, D, ρ and a have the same meaning as in

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of formula (1) and where both dye molecules together Carry 0 to 5 sulfo groups and 1 to 3 disazo groups of the formula

-N = N-Ar-N = N-Ar '(4)

or 1 disazo group of the formula (4) and one or 2 monoazo groups the formula

-N = N-Ar "(5)

or 2 disazo groups of the formula (4) and 1 monoazo group of the formula (5), with a chromium donating agent in the 1: 1 chromium complex and then this with the non-metallized Dye of formula (3) or (2) converts to the 1: 2 chromium complex.

The l: l complex of the azo dye is preferably formed of formula (2) and attaches the azomethine dye to these. Instead of the dye of the formula (3), there are azomethine dyes easily form, also the corresponding starting materials, i.e. amines of the formula

OH

[C0] _p (6)

D-NH ₂

and aldehydes of the formula

OH

(7)

are used, with any groups of the formula (4) and (5) bonded to the ring a and the radical D already in these starting products available.

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Instead of the groups capable of complex formation, the dyes of the formula (2) in particular can be converted into metallizable Substituents that can be transferred to groups, such as low molecular weight Wear alkoxy groups, especially methoxy groups, provided that they are used a metallizable group, e.g. a hydroxyl group, is formed during the chromating process. As a complex forming group are Hydroxyl groups preferred.

It is preferred to use azomethine compounds that only contain a radical of the formula (4) which is mainly in the 3- or 5-position of the ring a, i.e. in the o- or p-position to the hydroxyl group seated, with the p-position being preferred.

In the formulas (4) and (5), Ar, Ar ¹ and Ar "benzene or naphthalene ^{radicals, Ar 1} and Ar" also mean heterocyclic radicals, for example thiazolyl, benzthiaolyl, thiadiazolyl, benzisothiazolyl, imidazolyl, benzimidazolyl , Pyrazolyl, triazolyl, naphthothiazolyl, quinolinyl, pyridinyl, indazolyl, oxazolyl or benzoxazolyl radicals. The radicals Ar ¹ and Ar ″ can carry all substituents customary in diazo components; however, Ar and Ar ¹ are preferred, if appropriate with chlorine, bromine, nitro, sulfonamido and N-mono- or Ν, Ν-disubstituted sulfonamido groups, sulfone groups , low molecular weight alkyl or alkoxy groups substituted phenyl or naphthyl radicals, Ar is preferably a phenylene or naphthylene radical, the substituents mainly being low molecular weight alkyl and alkoxy radicals, such as methyl, ethyl and methoxy.

The dyes of the formula (2) can be prepared in a known manner by coupling. The remainder A can be a remainder of the Be benzene or naphthalene series and apart from the complex-forming series

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Group carry the usual substituents, such as chlorine, bromine, Cyano, nitro, low molecular weight alkyl, low molecular weight alkoxy, aryloxy, especially phenoxy, sulfo, sulfonamido and N-mono- or Ν, Ν-disubstituted sulfonamido groups, sulfonic groups, especially low molecular weight alkyl sulfone groups and acylamino groups.

The term "acylamino" refers here to amino groups, those with acyl residues of aliphatic or aromatic sulfon and in particular .carboxylic acids or of carbonic acid monoalkyl or -aryl esters are substituted. The term "acyl" thus includes low molecular weight alkanoyl, alkoxycarbonyl and alkylsulfonyl groups, such as the acetyl, chloroacetyl, propionyl, butyryl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or ethylsulfony groups, as well as aroyl, aryloxycarbonyl and arylsulfonyl groups, such as the benzoyl, chlorobenzoyl, methylbenzoyl, Nitrobenzoyl, phenoxycarbonyl, phenylsulfonyl or p-methylphenylsulfonyl group. Preferred acylamino groups are low molecular weight alkanoylamino, alkoxycarbonylamino or optionally substituted Benzoy! Amino groups.

Mono- or disubstituted sulfonamido groups are especially those with low molecular weight alkyl, hydroxyalkyl, alkoxy, alkyl, Cyanoalkyl, aralkyl, cycloalkyl, especially cyclohexyl, aralkyl, in particular benzyl or sulfonamide groups substituted by aryl radicals to call. The sulfonic groups are mainly low-molecular alkylsulfonyl, with hydroxyl, chlorine or low-molecular

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low molecular weight alkylsulfonyl, phenylsulfonyl, chlorophenylsulfonyl, methylphenylsulfonyl, Nitrophenylsulfonyl, methoxyphenylsulfonyl or benzylsulfonyl groups in question.

Suitable diazo components of dyes of the formula (2) are, for example, anthranilic acid, 4-sulfo- and 4-sulfonamidoanthranilic acid, 2-amino-l-hydroxybenzene, 2-amino-l-, ethoxybenzene, 4-chloro- and 4,6-dichloro-2-amino-1-hydroxybenzene, 4- or 5-nitro-2-amino-1-hydroxybenzene, 4-chloro- and 4-methyl- and 4-acetylamino-6-nitro- -2-amino-1-hydroxybenzene, 6-acetylamino- and 6-chloro-4-nitro-2-amino-1-hydroxybenzene-, 4-cyano-2-amino-1-hydroxybenzene, 4-methoxy-2-amino-1-hydroxybenzene, 2-amino-1-hydroxybenzene-5-methyl- and 5-benzyl sulfone, 2-amino-1-hydroxybenzene-4-methyl-, -ethyl-, -chloromethyl- and butyl sulfone, 5-nitro and 6-nitro-2-amino-1-hydroxybenzene-4-methyl sulfone, 2-Amino-1-hydroxybenzene-4- or -5-sulfamide, -sulf-N-methyl- and -sulf-N-ß-hydroxyethylamide, 2-amino- -l-methoxybenzene-4-sulfanilide, 4-methoxy-5-chloro-2-amino-1-hydroxy-benzene, 4-methyl-2-amino-1-hydroxybenzene, 4-chloro-5-nitro- -2-amino-l-hydroxybenzene, 3,4,6-trichloro-2-amino-l-hydroxybenzene, 6-acetylamino-4-chloro-2-amino-1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene, 4-nitro-2-amino-1-hydroxybenzene-5- or -6-sulfonic acid amide , 4- or 5-chloroanisidine, 4- or -5-nitroanisidine, 2-methoxy-5 -methylaniline, 2,5 -dirnethoxyaniline, 2 -amino -1 -hydroxybenzene-4-sulfanthranilide, 2-amino-1-hydroxybenzene-4- or 5-sulfonic acid, 4-nitro-2-amino-1-hydroxybenzene-5 or -6-sulfonic acid, 5-nitro or 6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 6-chloro-2-amino-1-hydroxybenzene-4-sulfonic acid, anisidine-4 or 5-sulfonic acid, l-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino

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^ -hydroxynaphthalene-ö-nitro ^ -sulfonic acid, 4- (2 '-, 3' or 4 ^f -sulfophenylazo) -2-amino-1-hydroxybenzene, 4- (3'sulfonamidophenylazo) -2-amino-1-hydroxybenzene , 4- (4'-phenylazophenylazo) -2-amino-1-hydroxybenzene.

The remainder B can be derived in particular from the following groups of coupling components:

-Naphthols, optionally with chlorine., Acylamino, amino, Sulfo-, sulfonamido, N-mono- or Ν, Ν-disubstituted sulfonamido groups and sulfonic groups are substituted, these groups having the same meanings as given above are.

-5-pyrazolones, which in the 1-position, optionally with chlorine, Nitro, low molecular weight alkyl and alkoxy groups, sulfonamido, N-alkylated sulfonamide groups, sulfone or, in particular, sulfo groups have substituted phenyl or naphthyl radical. -Acetoacetic anilides and benzoyl acetic anilides, which are in the anilide core optionally with chlorine, bromine, low molecular weight alkyl, alkoxy, sulfone, sulfonamido, N-mono- or Ν, Ν-disubstituted Sulfonamido groups and sulfo groups can be substituted. -Phenols with low molecular weight acylaraino groups and / or are substituted by alkyl groups preferably containing 1 to 5 carbon atoms and couple in the ο-position.

-2,6-dihydroxy-3-cyano- or carbonamido-4-alkylpyridine and 6-hydroxy-2-pyridones, those in the 1-position by low molecular weight, optionally substituted alkyl, e.g. methyl, isopropyl, β-Hydroxyaethyl, ß-Aminoaethyl or γ-Isopropoxypropyl substituted are, in the 3-position a cyano or carbonamido group and in the 4-position a low molecular weight alkyl group, in particular

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Carry methyl.

Examples of such coupling components are: 2-naphthol,

1,3- or 1,5-dihydroxynaphthalene, 2-naphthol-6-sulfonamide, 2-naphthol-6-ß-hydroxyethyl sulfone, 1-naphthol,
Acetylamino-7-naphthol, 1-propionylamino-7-naphthol, 1-carbomethoxyamino-7-naphthol, 1-carboaethoxyamino-7-naphthol, 1-carbopropoxyamino-7-naphthol, 1-dimethylaminosulfonyl-amino-7 -naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7- or 8-sulfosMure, l-naphthol-3-, -4- or - 5-sulfosMure, 4-acetyl-2-naphthol, 4-methoxy-l-naphthol, 4-acetyl-1-naphthol, l-naphthol-3-, -4- or -5-sulfonamide, 2-naphthol-3- , -4-, -5-, -6-, -7- or -8-sulfonamide, 5,8-dichloro-1-naphthol, 5-chloro-1-naphthol,
1,3-dimethyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 1- (2'-, 3'- or 4'-methylphenyl) -3-methyl-pyrazol-5 -one, 1-phenylpyrazolone-3-carboxylic acid,

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l-phenylpyrazolone-3-carboxamide, l- £ 2 ^! -, 3'- or 4'-sulfophenyl) -S-methyl-pyrazol-S-one, 1- (2 ^! -Or 4'-methoxyphenyl) -3-methyl-pyrazol-5-one, 1- (2 ' -, 3'- or 4'-chlorophenyl) -3-methyl-pyrazol-5-one, 1- (2'-, 3 ¹ - or 4 ^I -nitrophenyl) -3-methyl-pyrazol-5-one, l - (2'-, 5 ¹ - or 3 ¹ -, 4'-dichlorophenyl) -3-methyl-pyrazol-5-one, 1- (2 ^f -, 3 ¹ - or 4 ^f -Sulfaraoylphenyl) -3-raethyl -pyrazol-5-one, 1 - (2 ', 5'-dichloro-4 ^f - sulfophenyl) -S-methyl-pyrazol-S-one, l- (2'-, 3 ¹ - or 4 ^l -methylsulfonylphenyl) -3-methyl-pyrazol-5-one, acetoacetanilide,

Acetoacetanilide-4-sulfonic acid, Acetoacet-o-anisidide,

Acetoacet-o-toluidide,

Acetoacet-o-chloranilide, acetoacetanilide-3- or -4-sulfonamide, Acetoacet-m-xylidide,

Tetralol

4-methylphenol,

3-dialkylaminophenol, especially 3-dimethylamino and 3-diethylaminophenol,

4-butylphenol,

4-amylphenol, especially 4-t-amylphenol, 2-isopropyl-4-methylphenol, 2- or 3-acetylamino-4-methylphenol, 2-methoxycarbonylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylphenol, 2,4-dimethylphenol and 3,4-dimethylphenol * 2,6-dibydroxy-3-cyano-4-ynethylpyridine, 1-Methy1-3-cyano-4-aetby1-6-hydroxypyridone,

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l-phenyl-S-carbonamido ^ -methyl-ö-hydroxypyridone,

The largely preferred coupling component for the azo compounds of the formula (2) is β-naphthol.

For the preparation of the azomethine dyes of the formula (3) The amines of the benzene or naphthalene series described in the preparation of the azo dyes of the formula (2) are also suitable, which, in addition to the complex-forming OH or COOH group, have the usual substituents, such as chlorine, bromine, Cyano, nitro, low molecular weight alkyl, low molecular weight alkoxy, aryloxy, especially phenoxy, sulfo, sulfonamido and N-mono- or Ν, Ν-disubstituted sulfonamido groups, sulfonic groups and acylamino groups.

Suitable aldehydes of the formula (7) are, for example: 2-hydroxynaphthaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxybenzoaldehyde,
5-methyl-2-hydroxybenzaldehyde,

3,5-dimethyl-2-hydroxybenzaldehyde,
5-butyl-2-hydroxybenzaldehyde,
5-chloro- or -bromo-2-hydroxybenzaldehyde, 5-sulfo-2-hydroxybenzaldehyde,
3,5-dichloro-2-hydroxybenzaldehyde,
3-chloro-5-methyl-2-hydroxybenzaldehyde, 3-methy1-5-chloro-2-hydroxybenzaldehyde, and especially the corresponding, in the 3- or 5-position with an azo or disazo group of the formula (4) or ( 5) substituted aldehydes. The introduction of an azo or disazo group in the ο-hydroxyaldehydes mentioned is done in the usual way by

~> _J A "t! XT "T

one connects Ar'-N = N-Ar-N2 or Ar '^ Nn with a

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Aldehyde couples.

These compounds are preferably derived from naphthylamines and in particular anilines, such as ot-naphthylamine, 4,8-disulfo-ß-naphthylamine, 6,8-disulfo-ß-naphthylamine, a-naphthylamine-4- or 8-sulfonic acid, m-aminobenzene sulfamide, aniline, 2-, 3- or 4-sulfoaniline, 4-nitroaniline, toluidine, anisidine, 4-chloroaniline, 4-chloro-3-sulfoaniline, 4-nitro-2-sulfoaniline, 4-methyl--3-sulfoaniline or 2-nitro-4-sulfoaniline.

The preferred group of dyes according to the invention are those of the formula

Κ © (8)

A ¹ —N = N— B '

A ¹ and D ^1, independently of one another, each have a phenyl or naphthyl radical optionally substituted by sulfonamido, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, in particular the methyl sulfone group, chlorine, bromine, cyano, nitro, low molecular weight alkyl and low molecular weight alkoxy B ^{1 is} a phenyl radical optionally substituted in the 4-position with low molecular weight alkyl or acylamino, a naphthyl radical optionally substituted with chlorine, sulfonamido, or sulfonamido, mono- or disubstituted sulfonamino or sulfone groups, acylamino groups, in particular the β-naphthyl radical, the Rest of one

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l-Aryl-S-methyl-pyrazole-S-ones or the remainder of one in the anilide core optionally with sulfo-, nitro-, sulfonamido-, mono- or disubstituted ones Substituted sulfonamido or sulfone groups, chlorine, bromine, low molecular weight alkyl and low molecular weight alkoxy Acet- or benzoylacetic anilide, Ar, an optionally with low molecular weight alkyl or alkoxy substituted phenylene or a naphthylene radical which is optionally substituted by sulfo and

Ar-I one optionally with chlorine, bromine, nitro, sulfo-, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups low molecular weight alkyl or alkoxy groups substituted phenyl or naphthyl radical and K is a cation.

Of particular interest for the dyeing of leather

among the dyes according to the invention are those of the formula

S ₇ -PI

N = N-

κΦ

(9)

the radicals S ,, S ^, So and S, each hydrogen, sulfo-, sulfonamido-, mono- or disubstituted sulfonamido or methyl sulfone groups, Nitro, cyano, chlorine, bromine, low molecular weight alkyl or low molecular weight alkoxy and are those of the formula

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₂ Θ

(10)

N = N-Ar ₁ -N = N-Ar '

where So and S, the same as above, S ₁ - hydrogen or nitro and B "denotes the residue of an α-naphthol, β-naphthol or a 1-aryl-3-methyl-5-pyrazolone. Ar, and Ar- have The meaning given for formula (8) is also important because of its good accessibility and coloring properties in the groups of preferred dyes mentioned, especially those

the formula

Ν. «Ν -Ar ^ -N = N-Ar ¹

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K θ (H)

2K $

(12)

N = N-Ar ₁ -N = N-ArJ

wherein the benzene rings b and c independently each with a nitro, methylsulfonyl or sulfo group or with a nitro and methylsulfonyl or sulfo groups are substituted, S ^ hydrogen or nitro and Ar,, Ar | and K are the same as in Formula (8).

These preferred dyes should be per complex molecule contain one to three sulfo groups.

The conversion of the monoazo dye of the formula (2) or the azomethine dye of the formula (3) into the 1: 1 chromium complex is carried out by conventional methods known per se, for example by treating in an acidic medium with a salt of trivalent chromium, such as chromium formate, chromium sulfate , Chromium chloride hexahydrate or chromium fluoride, at the boiling point or optionally at temperatures exceeding ^{10O 0 C.} Trivalent chromium can also be produced in the reaction mixture of chromium VI compounds, eg chromate, if a reducing agent is added at the same time. The metallization can be in aqueous, organic-aqueous

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or in purely organic solvents such as alcohols or Ketones.

The reaction of the 1: 1 chromium complex of the dye of the formula (2) or (3) with the metal-free dye of the formula (3) or (2), respectively. The one-pot reaction between a 1: 1 chromium complex of a dye of the formula (2), an amine of the formula (6) and an aldehyde of the formula (7) is conveniently carried out in a neutral to slightly alkaline medium, in an open or closed vessel, at an elevated temperature , for example at temperatures between 50 and 120 ⁰ C. It can be in organic solvents, such as alcohols or ketones or work in v'ässriger solution, can promote additions of solvents such as from alcohols, formamide, etc., optionally the reaction. In general, it is advisable to react equivalent amounts of the chromium-containing 1: 1 complex and the metal-free dye with one another, the molecular ratio between the metal-free dye and the 1: 1 complex being advantageously at least 0.85: 1 and at most 1: 0.85; an excess of metal-containing dye generally has less of a disadvantageous effect than an excess of metal-free dye. The closer this ratio is to 1: 1, the more advantageous the result in general.

The new, chromium-containing ones obtainable by the above processes Mixed complexes are advantageous in the form of their salts, in particular alkali, especially sodium, or ammonium salts or salts of organic amines with positively charged nitrogen atom isolated. They are suitable for coloring organic Materials of the most varied kinds. The water-insoluble dyes are mainly used for dyeing textile material

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Polyamide and also for dyeing paints and varnishes, paper, viscose, polyamide, cellulose ether and cellulose ester spinning masses.

They are used for dyeing and printing textile material used in dispersed form, it being possible to use the customary dispersants.

The water-soluble dyes are mainly leather and textile dyes and are suitable for dyeing wool and silk, also of casein, super polyamide and super polyurethane fibers and especially for dyeing leather and furs. The new dyes can also be used for printing on the materials mentioned. Above all in the form of their alkali salts, e.g. sodium or potassium salts, they are readily soluble in water and for dyeing from neutral or weakly acidic, e.g. acetic acid bath. Dyestuffs in particular are used for dyeing and printing textile materials with 1 to 3 sulfo groups, while those with 4 and 5 sulfo groups are also suitable for leather. The dyes can contain the usual coupons and with the usual Aids to be colored. When dyeing textiles with dyes that contain more than 1 sulfo group, we recommend the Addition of a leveling aid ... e.g. UNIPEROL or ALBEGAL A.

The new dyes are distinguished above all by their good hiding power on leather combined with good fastness properties. They give level dyeings with good light, washing, water, perspiration, alkali, acid, diffusion and rub fastnesses. Dyes with high light and wet fastness properties can also be obtained on materials made of polyamide. The result is markedly strong, yellow-brown to dark brown nuances.

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In the following examples, unless otherwise stated, parts are parts by weight and percentages Percentages by weight and temperatures are given in degrees Celsius.

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example 1

3 ^Ό 3 Na

42.4 parts of the monoazo dye from diazotized l-amino-2-hydroxynaphthalene-4-sulfonic acid and l-phenyl-3-methyl-5-pyrazolone are mixed with 26.65 parts of chromium chloride hexahydrate in 500 parts by volume of ethylene glycol at 120 ° to 125 ° C stirred until the starting compound has disappeared. The solution of the chromium complex dye of the type 1 atom of chromium: 1 molecule of dye is then mixed with 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene, 41 parts of coupling ^{product of diazotized 4-amino-azobenzene-3 l} -sulfonic acid and salicylaldehyde and 80 parts by volume of 20% sodal solution and a further 1 to 2 hours at 80 to 85 ° C for the purpose of accumulation

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stirred. After the reaction has ended, the asymmetric chromium-containing dye by adding saturated sodium chloride solution precipitated, filtered off and dried. It represents a brown powder that dissolves in water with red-brown Dye dissolves and dyes leather from a weakly acidic bath in red-brown shades of generally good fastness properties.

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Example 2

SO.

2 ° 2Na

30.9 parts of the diazotized monoazo dye 5-nitro-2-amino-1-hydroxy-benzene and 2-hydroxynaphthalene are suspended in 500 parts by volume of ethylene glycol. After adding 26.65 parts of chromium chloride hexahydrate, at 120 Stirred to 125 ° C until the starting compound has disappeared. The solution of the chromium complex dye type 1 atom chromium: 1 molecule of dye is then mixed with 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene, 41 parts of coupling product from diazotized 4-aminoazobenzene-3'-sulfonic acid and salicylaldehyde and 80 parts by volume of 20% soda solution and stirred for a further 1 to 2 hours at 80 to 85 ° C for the purpose of attachment.

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After the reaction has ended, the asymmetric chromium-containing dye is obtained by adding saturated sodium chloride solution precipitated, filtered off and dried.

It represents a dark powder that dissolves in water with a brown color and wool or polyamide material as well Dyes leather from a weakly acidic bath in brown shades of generally good fastness properties.

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Example 3

O- ■ -0.

NO

N = N

SO ₃

3 ^

3Na

43.9 parts of the complex chromium compound of the type 1 atom of chromium are suspended in 1000 parts of water: 1 molecule of dye, which contains 5.2 parts of chromium and 38.9 parts of mono- "azo dye from diazotized ^ nitro ^ -amino-1-hydroxybenzene- 6-sulphonic acid and 2-hydroxynaphthalene corresponds with 41 parts of coupling product of 4-aminoazobenzene-3'-sulfonic acid and salicylaldehyde and 15.4 parts of 4-nitro-2-amino-l-hydroxybenzene. the mixture is heated to 80 to 85 ° C and simultaneously increases ¹ constant pH is completed by further addition of sodium carbonate solution 20% and the addition reaction the pH of the suspension to 7 to 7.5 by addition of sodium carbonate solution 20% and keeps it so long as at this temperature and the like. the new chromium-containing

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Dye is precipitated by adding sodium chloride; it is filtered off and dried. After drying it represents a dark powder that dyes polyamide material or leather from weakly acidic bath in real brown tones. These dyeings show good fastness properties.

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- · 24

Example 4

NO

O "S

Cl

N = Ν-

N = N

3 ^f 3 Na

38.9 parts of the monoazo dyestuff obtained from diazotised 4-nitro-2-amino-l-hydroxybenzene-6-sulfonsä * acid and 2-hydroxynaphthalene are stirred with 26.65 parts of chromium chloride hexahydrate in 500 parts by volume of ethylene glycol as long as at 120 to 125 ⁰ C until the Output connection has disappeared.

The solution of the chromium complex of the type 1 atom of chromium 1 molecule of dye is then mixed with 19.2 parts of 3,5-di-chloro-6-hydroxybenzaldehyde, 39.7 parts of 3-amino-4-hydroxy-4 ^! (4 "sulfo · phenylazo) azobenzene, obtained by coupling diazotized 4-aminoazobenzene-4'-sulfonic acid with 2-acetylamino-1-hydroxy-

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- ■ - '25 -

benzene and saponification of the acetylamino group in an alkaline medium, 80 parts by volume of 20% soda solution and ^{stirred for a further 1 to 2 hours at 80 to 85 0} C for the purpose of attachment. After the reaction has ended, the finished, chromium-containing dye is precipitated by adding saturated sodium chloride solution, filtered off and dried.

It represents a dark powder that dissolves in water with a brown color and wool or polyamide material as well Dyes leather from a weakly acidic bath in brown shades of generally good fastness properties.

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Example 5

= N

SO,

2 Θ

2 Well

35.9 parts of the complex chromium compound of the type 1 atom of chromium: 1 molecule of dye, which diazotized 5.2 parts of chromium and 30.9 parts of monoazo dye, are suspended in 100Q parts of water! 5-Nitro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene correspond to 12.2 parts of salicylaldehyde and 39.7 parts of 3-amino-4-hydroxy-4 ^r (4 "sulfophenylazo) azobenzene and 18 parts of sodium carbonate in the form of a 20% aqueous solution. The mixture is heated to 80 to 85 ° C. and kept at this temperature until the starting substances have disappeared. The new, chromium-containing dye is precipitated by adding sodium chloride; it is filtered off and dried to the

508 8.4 7/1072

Drying it produces a dark powder that dissolves in water with a brown color, and leather from a weakly acidic bath in brown-black tones.

If the azo and azomethine components given in the table below are used, 1: 2 chromium complexes with similar properties are obtained which dye leather in the nuances given in the last column.

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Aer Fornel dye (2) Dye of formula (3)

nuance

OH

OH

OCH,

OH

N = N

OH OH

N = H-,

10.

^C 5 ^H 11 OH

N ~ N

OH

N = N

N0 "

OH

OH

CN I

^CH 3

OH

HO ₃ S

do

do

do

do

do

do

do

do

Brown Brown

Olive brown

Brown Yellow-brown Brown

Brown

Brown

Brownish red

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-I , 1

nuance

ΪΟ

^CH 3

OH

OH OH

SOJ SC, H

J J

OH

HO ₃ Sγ * γ N

OCH ₃ 14 A ^ - N

OH

OH

OH

OH

0 «

do

do

do

-N

do

do

do

Brownish red

Brown

Brown

Brown

SO ₃ H

Brown

Brown

Red-brown

Brown

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No. nuance

OH

OH

^0H

"° 3 ^S

OH

OH OH

° 2 ^C 5 ^H 11

OH

OH

C0-NH

OH

SO ₃ H

do

do

do

do

do

do

SOY

Brown

Brown

Brown

Brown

Brauns ti chi g-ge1b

Brownish tint gslb

Brownish tinge-orar.ge

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nuance

OH

N-N-

OCH ₃ ^ÜH

HO.

OH

N N

HO.S

OH N »N-A,

NO _n

OCH ₃ OH

N = B-

' ^CH 3 ⁵⁰ 3 ^H

OH

do

do

do

do

do

do

SO ₃ H

Brown

Brown

Red-brown

Brown

Brown

Brown

Brown

Brownish tint orar.ge

50 9 847 / Ί 072

nuance

OH

OH

N-C

OH

OH

CO-NH

NO ₂

J!

- ^ s

QH

OH

OH

OH

OH

OH

OH NO,

OH

OH

CH.

OH

OH

NO ₂

SOY

Wl ₂

■ ^b Cl

do

do

OH OH

(Y «φ

N0 "N = N-

-Q-

do

do

OH

Brownish orange

Brownish orange

orange

Brownish red

Brown

Brown

Brownish red

⁹ X

do

Brown

509847/1072

nuance

HO.

K «N

OH ι

OH

CH-

HO.

OH

N - K

OH

OH
2 ^ C-CH,
- NC * ³
CO-NH
O OH
- ,. χ. OH
- ¹ O τ
VI «Τ"

CH,

HO.

OH

N - N-

SO ₃ H

OK OH

SO ₃ H

do

do

do

do

do

Brown brown

Brownish orange

Brown Braunroi

Brown

Brown

509847/1072

nuance

HO ₃ S

OH

N-K-

OH

OH

OH

CH,

OH

^l0 3 ^!

OH

NO _n

N - N-

OH

N (L

CO-NH

COOH OH

do.

do

do

do

do

Brown

Brown orange red

Orange-brownish tinge

Brown orange

509847/1072

nuance

OH Ψ

OH

OH

" ⁰ Z

OH OH

ότ-φ

OH N - N-

HO.

OH

HO ₃ S

N - N--

OH

OH

HO.

N-N-

HO S> ^^ v / N = N-

OH

OH

CH-

Brown brown

Brown

Brown brown brown

Brown

Brownish red

Brown-

509847 / 1.0 72

2520b2b

nuance

OH

HO.

N-N

NO,

HO.

OH

HO ₃ S

OH

N- N

KO ₂

OH I

OH

HO.

CH.

OH OH

H0, S,

VI

N-C CO-I

OH

J -CH ₃

OH

SOY

■ ^K O - »=» - O

Brown

KO ₂ IWi

do

do

do

do

do

do

Brown

Brown

Brown

Brownish red

Brown

Brownish orange

Brown

509847/1072

nuance

OH OH

Cl SO ₃ H

^ ¹ ■ ^N

SO ₃ H

OH

OH

OH OU

(Jr ¹ -φ

Vn

OH

Κ - N

N - N

HO.

N-N

NO.

OH

N0 "

OH

Brown

To ₂

do

Brown

OK

SOY

Brown

. N

do

Brown

OH

SO.H

Brown

do

Brown

do

Brown

do

Brown

509847/1072

nuance

OH

OH

NO,

OH

OH

HO

K «Ν

HO.

OH

K-H

KO _n

OH

OH

CN «3

HO.

HO, S

N-N

OH

do

do

do

T,

do

do

Brown

! O ₃ H

Violet brown

Dark brown dark brown

Brown-red brown

Brown

509847/10 72

Üuance

OH

OH

"ψ-

OH OH

-N

(V — ό '- "Cu.ay

Brown

do

Brown

OH

do

Brown

OH

OH

HO

SO-H

Brown

OH

OH

OH OH

do

Brown

do

Brown

! O ₂ C ₅ H _n

do

Olive brown

OH

OH OH

Brown

OH

do

Brown

509847/1072

fJuance

Oh

NO,

OH

OH OH -N - N-

¹⁰ 2 ^C 5 ^H 11 OH

HO.

* G0

3 OH

N - N-

OH

OH

N «N

HO ₃ S.

pH

OH

HS

OH OH

^U 3

^C 5 ^H 11

OH

N - N

OH

OH

SO ₃ H

Olive brown

N0 "

do

do do

do

do do

do

do do

Brown

Brown

Brownish red

Brown

Brown

Brown

Brown

Brown

Brown

509847/1072

Uuance

- «/ ΙΟ

OH

OH OH

«Ο ₂

OH

OH

^0Η

T CO-fiH

OH

OH OH

'■ Ό-.

OK

Orange brown

do

OH

SO ₂ CH ₃ do

do

do

do

do

do

do

Brown

O ₃ H

Brown

-0

Brown

Brown

Brown

Brown

Brown

Yellowish brown

Brown

509847/10

CO-W

OK OH

ι;

¹ OO

Cl

OK OH

OH

«J

Cl OH

sb_H

N-N-,

^C S »"

OH

«O ₂ OH

OH

NO,

OH

OK OH

: N

S0_H

SO ₂ CH ₃

OH

; o ₃ h

nuance

SO ₃ H

Yellow-brown

Brown

Brown

Red-brown

Brown

Brown

Brown

Brown

Brown

Brown

509847/1072

nuance

OH

HQ S

OH

ης λ ^Ν - ^Ν

⁰ ^

NO ₀

OH

0 »

OH

OH

OH

N-N

NOn

OH

N N

NOo

OH OH

OH OH

-N - N-

Cl.

OH

OH

OH

CH-

OH

OH

SO ₃ H

Brown

do

Brown

do

Brown

Brown

SO ₃ H

do

Brown

-α.

Brown

do

Brown

do

Brown

OH

OH

Brown

N .N

B098A7 / -1O72

ZOZUOZD

No. Nuance

OH OH

-N «N-

OH

N-N-

KO ₀

OH

OH

OH

NO

OH

OH

OCi

OH

OH

OH

CH-

■ A

SO ₃ H

Brown

Brown

Brown

Bcaun

Brown

Brown

Brown orange

Brown

3raun

5098 ^ 7/1072

K'jar.ce

OH

OH

HO ₃ S

N - N

OH

N- N

NO ..

OH

OH

OH

, φ

OH

N-N

NO ₂ OH

OH

OH

OH

OH

VI

OCI

OH

HO.

OH

N-N

OH

'■ Ό --.- 0

Brown

COOH

(Jr ¹ "

do

do

do

do

do

do

do

do

Brown

Brown

Brown

SOH

Brown

Olive brown

Brown

Brown

Olive brown

Brown

509847/1072

Huar.ce

OH

SO ₃ H

N-N

OH

H-K

OH

Λ JL η- Κ

CH

OH

OH

CO-KH

OH

OH

N-C '

CO-N ¹ H

COOH ^CH

do

do

do.

do

do

do

SO ₃ H

Brown

Brown

Brown

orange

Brownish red

Braunstichiq gel: Brownish tinge g-GeH

509847/1072

For the dye-el (2)

- 47 -

Coloring formula (3)

huar.ce

OH ΌΗ

N0 "

OH OH

UH UH

OH OH

^H 3 ^S

OH OH

L Cf

OH OH

NO,

OH OH

Φ-

167

OH OH

■ Ν =

"2 ^C 5 ^H 11

OH OH

N = CH

N = N

tx-

do.

do.

do.

do.

N = CH

do.

do.

So ₃ K

509847/1072

Dye of formula (2) Dye of formula (3)

nuance

OH OH

"2 ^C 5 ^H 1

OH OH

OH OH

OH OH

HO ₃ S

«Ν

OH OH

= N

OH OH

V-S5

OH OH

N = CH ■

3

do.

OH OH

N = CH

SO ₃ H

SO ₃ H

do.

do.

OH OH

-φ

COOH

-ό

= H

do.

509847/1072

Dye of the formula (2) Dye of the formula (3)

HO ₃ S

OH OH

N «N

OH OH

N = N '

176

SOY

OH

OH

177

SO ₃ H

N = N

HO ₃ S

OH OH

N = N

OH OH N =

OH OH

N =

SO ₃ H

N0 "

HO ₃ S

N = N

182

N0 "

OH OH

N »N

HO ₃ S

SO ₀ COOH N = N

SO ₃ H

N = CH

■■ tX

^Cl

OH OH

SO ₃ H

SO ₃ H

do.

do.

N = CH

do.

do.

509847/1072

Dye of For-el (2) Dye c _Sr Formula (3)

Kuanes

OH OH

N = Ν

SO ₃ H

OH OH

OH OH

SO ₃ H

N0 "

do.

ISO-H

OH OH

OH OH

Ho ₃ p

N0 "

N = N

SO ₃ H

do.

N = CH

N = N

OH OH

-α

SOY

do.

do.

N = CH

CO

509847/1072

Color rule for wool:

100 parts of woolen knitting yarn are introduced at 50 ° into a dyebath containing 2 parts of the dye of the example in 4000 parts of water 3, 4 parts of ammonium sulfate and 2 parts of a leveling aid means contains. The liquor is brought to the boil in the course of 45 minutes and at this temperature for a further 45 minutes left. The dyed material is then removed, rinsed thoroughly with cold water and dried.

Dyeing instructions for leather:

100 parts of clothing suede (dry weight) are aufgewalkt at 50 ⁰ C in a solution of Looo parts of water and 2 parts of 24% ammonia for 2 hours and then at 60 ⁰ C in a solution of 1000 parts of water, 2 parts ammonia 247oig and 6 parts Dye of Example 1 colored for 1 hour. A solution of 40 parts of water and parts of 85% formic acid is then added and dyeing is continued for a further 30 minutes. The leathers are then rinsed thoroughly and, if appropriate, treated ^{with 2 parts of a dicyandiamine formaldehyde condensation product at 50 ° C. for 30 minutes.}

Other suede and glove leather can be dyed in the same way.

509847/1072

Claims (31)

Claims 1; 2-chromium complex dyes of the formula Oi = N-Ar-N = N-Ar ') - (N = N-Ar ") (1) (so A is the remainder of a diazo component of the benzene or naphthalene series, which is the complex-forming group X in position to Azo group carries, B the remainder of a coupling component coupling in the o-position to the oxy group means, D is the remainder of an amine of the benzene or naphthalene series, which is the complex-forming group in ο-position to the azo group wearing, X is an oxygen atom or a -CO-0 group, Ar is an aromatic, carbocyclic radical, Ar 'and Ar "is an aromatic, carbo- or heterocyclic radical, q is an integer from 0 to 5, η is an integer from 1 to 3 ₅ m is an integer from 0 to 2 and ρ 0 or 1 509847/1072 mean, where η + m may be at most 3 and where the benzene ring a can carry a further fused-on benzene ring or be substituted by halogen, nitro, alkyl and alkoxy and K is a cation. 2. A chromium complex dye according to claim 1, wherein B is a radical of the benzene or naphthalene series, the radical of a pyrazol-5-one, a pyridone or an acet- or benzoyl acetic anilide. 3. Chromium complex dyes according to claims 1 and 2, wherein m = O and n = 1 and the group of the formula -N = N-Ar-N = N-Ar '(4) is bound to the azomethine component. 4. A chromium complex dye according to Claims 1 to 3, in which the disazo group of the formula (4) is in the 5-position on the benzene ring a is bound. 5. Chromium complexes according to Claims 1 to 4, in which Ar is a radical from the benzene or naphthalene series and Ar ¹ and Ar "each mean a radical from the benzene or naphthalene series or a heterocyclic radical. 6. Chromium complex dyes according to Claims 1 to 5 of the formula 509847/1072 Κ © (8) where A ¹ and D 'are each independently a phenyl or naphthyl radical optionally substituted with sulfo-, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, chlorine, bromine, cyano, nitro, alkyl and alkoxy, B' is a 4 -Position optionally substituted with alkyl or acylamino phenyl radical, a naphthyl radical optionally substituted with chlorine, sulfonamido or sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, acylamino groups, the radical of a 1-aryl-3-methyl-pyrazol-5-one or the remainder of an acetal or benzyl acetic anilide optionally substituted in the anilide nucleus with sulfo-, nitro, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, chlorine, bromine, alkyl and alkoxy, Ar, a phenylene optionally substituted with alkyl or alkoxy or a naphthylene radical which is optionally substituted by sulfo and Ar | denotes a phenyl or naphthyl radical optionally substituted with chlorine, bromine, nitro, sulfo-, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, alkyl or alkoxy groups, and K is a cation. 509847/1072 7. Chromium complex dyes according to Claims 1 to 6, the formula κΦ (9) wherein the radicals S- ,, S ^, S ~ and S, each hydrogen, sulfo-, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, nitro, cyano, chlorine, bromine, alkyl or alkoxy and B ¹ , Ar and Arj mean the same as in claim 6. 8. A chromium complex dye according to Claims 1 to 5 of the formula 0 '
CO = N - B ¹ O -N = CH- ^ N N = N- Ar ₁ -N = N- Ar [ (13) 509847/1072 wherein S. and S ~ the same as in claim 7 and KJ B ¹ , Ar, and Ar.! mean the same as in claim 6. 9. Chromium coraplex dyes according to Claims 1 to 6 formula ? 5 ° 3 ^S \ _ / ~~ ^{N = N} - f ' : cr 3-0 "" ^{= CH} - ^ 2K® (10) S ~ and S, which have the meaning given in claim 7, S _{5 is} hydrogen, chlorine, bromine, sulfo, or nitro, B "is the remainder of a c-naphthol, β-naphthol or l-aryl-3-methyl-5- means pyrazolons and Ar ,, Arj and K are the same as in claim 6. 10 · Chromium complex dyes according to claims 1 to 5 of formula 5098 4 7/1072 21 <θ (H) wherein S ₁ - and B "are the same as in claim 9 and Ar,, ArJ and K are the same as in claim 6. 11. A chromium complex dye according to claims 1 to 10, wherein B, B ¹ or B "is the radical of a β-naphthol. 12. Chromium complex dyes according to claims 1 to 7 of the formula N = N Cr N = N = N-Ar ₁ -N = N-Ar [509847/1072 _κ θ (H) wherein the benzene rings b- and c, independently of one another, each with a Sulfo-, methylsulfonyl or nitro group or with a sulfo- or methyl sulfonyl and nitro group are substituted and K, Ar. ,, and ArI mean the same as in claim 6. 13. Chromium complex dyes according to Claims 1 to 6 and 10 of the formula , 0 = N- Ar ₁ -N = N 2 K (12) wherein S1 is hydrogen or nitro and the benzene ring c is substituted with a sulfo, methylsulfonyl or nitro or sulfo or methylsulfonyl and nitro group and Ar ,, ArI and K are the same as in claim 6. 14. Chromium complex dyes according to Claims 1 to. 12, which contain 1 to 3 sulfo groups per complex molecule. 15. Process for the preparation of 1: 2 chromium complex dyes the formula 509847/1072 »59 - ^ = N-Ar-N = N-Ar ¹ ) N = N-Ar ") do κθ A is the residue of a diazo component of the benzene or naphthalene series which has the complex-forming group X in the o-position to the azo group wearing, B is the remainder of a coupling component coupling in the o-position to the oxy group means, D is the residue of an amine of the benzene or naphthalene series, which is the complex-forming group in the o-position to the azo group wearing, X is an oxygen atom or a -COO group, Ar is an aromatic, carboxyclic radical, Ar ¹ and Ar "each represent an aromatic, carbo- or heterocyclic radical, q is an integer from 0 to 5, η is an integer from 1 to 3, m is an integer from 0 to 2 and ρ O or 1 mean, where n + m may be at most 3 and in which the benzene ring a can carry a further fused-on benzene ring or can be substituted by halogen, nitro, alkyl and alkoxy and K ⁺ 509847/10 7 2 is a cation, characterized in that a dye of the formula (2) A-N = N-B XH-OH or a dye of the formula (3) (3) where symbols A, B, X, D, ρ and a are the same as in formula (1) mean and where these two dye molecules together 0 to sulfo groups and 1 to 2 disazo groups of the formula (4) -N = N- Ar -N = N- Ar (4) or a disazo group of the formula (4) and a monoazo group of the formula (5) -N = N- Ar "(5) contained, converted into the 1: 1 chromium complex with a chromium-releasing agent and this subsequently with the non-metallized Dye of formula (3) or (2) converts to the 1: 2 chromium complex. 16. The method according to claim 15, characterized in that a dye of the formula (2) is converted into the 1: 1 chromium complex and then with an azomethine dye of the formula (3) or with a mixture of an amine of the formula (6) OH [CO] ι Ρ D - _2nd 509847/10 7 2 and an aldehyde of the formula (7) OH ^CH0 converts, with any groups of the formula (4) or (5) bonded to the ring a or the radical D already in the starting products available. 17. The method according to claims 15 and 16, characterized in that that one starts from a dye of the formula (2) in which B is a radical of the benzene or naphthalene series, the radical of one Pyrazol-5-one, a pyridone or an acet- or benzoyl acetic anilide is. 18. The method according to claims 15 to 17, characterized in that that an azomethine dye of the formula (3), which is a group of the formula (4) -N = N-Ar -N = N-Ar '(4), and a monoazo dye of the formula (2) is used. 19. The method according to claims 15 to 18, characterized in that that one starts from an azomethine dye of the formula (3) in which a disazo group in the 5-position of the benzene ring a of formula (4) is bound. 20. The method according to claims 15 to 19, characterized in that that one starts from azo and azomethine dyes, in which Ar is a radical of the benzene or naphthalene series and Ar 'and Ar "is one radical each from the benzene or naphthalene series or one 509847/1072 mean heterocyclic radical. 21. The method according to claims 15 to 20, characterized in that one of a monoazo dye of the formula A ¹ -N = NB ¹ OH OH and an azomethine dye of the formula OH ^0H where A ¹ and D 'are each, independently of one another, a phenyl or naphthyl radical optionally substituted with sulfo, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, chlorine, bromine, cyano, nitro, alkyl and alkoxy, B ^{1 is} a 4 -Position phenyl radical optionally substituted with alkyl or acylamino, a naphthyl radical optionally substituted with chlorine, sulfo-, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups and acylamino groups, the radical of a 1-aryl-3-methyl-pyrazol-5-one or the remainder of an acetic or benzoyl acetic anilide, ar- or benzoyl acetic anilide optionally substituted in the anilide nucleus with sulpho-, nitro, sulphonamido, mono- or disubstituted sulphonamido or sulphone groups, chlorine, bromine, alkyl and alkoxy. an optionally substituted with alkyl or alkoxy phenylene or an optionally substituted with sulfo naphthylene radical and Ar, 'one optionally substituted with chlorine, bromine, nitro, sulfo, sulfonamido, mono- or disubstituted sulfonamido or sulfone groups, alkyl or alkoxy group Phenyl 509847/1 072 or naphthyl radical. 22. The method according to claims 15 to 21, characterized in that that one of a monoazo dye of the formula 2 ~ Xjl-N = NB ¹ (17) ° ^H starts out, wherein S, and S ^ each hydrogen, a sulfo, sulfonamido, mono- or disubstituted sulfonamido or sulfone group, nitro, cyano, chlorine, bromine, or alkyl or alkoxy and B ^{1 has the} same meaning as in claim 21 . 23. The method according to claims 15 to 21, characterized in that that one of a monoazo dye of the formula (18) starts out, wherein B "is the remainder of an α-naphthol, β-naphthol or l-Aryl-3-methylpyrazolons means and Sf- hydrogen, chlorine, Is bromine, sulfo, or nitro. 24. The method according to claims 15 to 2_>, characterized in that that one of an azomethine dye of the formula 509847/1072 OH OH
I. c \ A. 3 ~ t J V ^S 4 I.
N = N-Ar ₁ -N = N-Ar ^ -N = CH- (19) goes out, where S "and S are hydrogen, sulfo, sulfonaraido, raono- or disubstituted sulfonamido or sulfone groups, nitro, cyano, Are chlorine, bromine or low molecular weight alkyl or alkoxy and Ar and ArJ are the same as in claim 21. 25. The method according to claims 15 to 20, 2 2 and 23, characterized characterized in that one of an azomethine dye of the formula ΓίΗ COOH j
AN = CH -Aj '· ₍₂₀₎ N = N- Ar ₁ -N = N- Ar ', where Ar ₁ and ArJ are the same as in claim 21. 26. The method according to claims 15 to 25, characterized in that that one starts from an azo dye in which B, B 'or B "is β-naphthol. 27. The method according to claims 15 to 23, characterized in that that one of an azo dye of the formula 509847/10 7 2 (21) or = N (22) and an azomethine dye of the formula (23) -N = N- starts in which the benzene rings b and c are each independently substituted with a sulfo, methylsulfonyl or nitro group or with a sulfo or methylsulfonyl and nitro group, S1 is hydrogen or nitro and Ar, and ArJ are the same as in claim 21. 28. The method according to claims 15 to 27, characterized in that that one starts from an azo and an azomethine dye which together contain 1 to 3 sulfo groups. 29. Process for dyeing and printing materials made of natural or synthetic polyamides using the 509847/10 7 2 dyes defined according to claims 1 to 14. 30. The method according to claim 29, characterized in that to dye leather. 31. The according to claims 29 and 30 obtained, colored or printed material. 509847/10 7 2